Ink For Ink-Jet Recording

ABSTRACT

An ink for ink-jet recording contains a copper phthalocyanine pigment as a colorant, and a benzotriazole compound. The ink further contains a metallic phthalocyanine compound having one or more counter ions, wherein about 2 mol % to about 20 mol % of the counter ions is ammonium ion and/or organic ammonium ion.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of Japanese Patent Application No.2006-252232, filed Sep. 19, 2006, which is incorporated herein byreference in its entirety.

BACKGROUND

One important characteristic of an ink for ink-jet recording is goodozone resistance. This means to prevent discoloration (degradation ofimage quality) of printed matter by ink-jet recording attributable tocontact with the ozone in air. Copper phthalocyanine dyes, which oftenare used as colorants for cyan colored inks, have good light fastness ascompared with dyes typically used for magenta and yellow colors.However, many copper phthalocyanine dyes have inadequate ozoneresistance. Some copper phthalocyanine pigments have been developedwhich have good light fastness as well as ozone resistance.

In ink for ink jet recording, an anticorrosive agent such as abenzotriazole compound is added to prevent corrosion of metallicmaterials that are brought into contact with the ink in the ink passageof ink-jet head. However, when an anticorrosive agent such as abenzotriazole compound is added to ink having a copper phthalocyaninepigment as a colorant, precipitates are created.

SUMMARY

An ink for ink-jet recording may have good corrosion resistance, goodozone resistance, and avoid generating precipitates even when a copperphthalocyanine pigment is used as a colorant and a benzotriazolecompound is used.

DETAILED DESCRIPTION General Overview

It was found that one or more of the above aspects may be achieved byadding, to ink-jet recording ink using a benzotriazole compound and acopper phthalocyanine pigment as a colorant, a metallic phthalocyaninecompound having one or more counter ions, wherein ammonium ion, organicammonium ion, or combinations thereof accounts for a specific ratio ofthe counter ions.

Illustrative Aspects

Illustrative aspects will be described. These aspects merely provideexamples and it is needless to say that the aspects can be suitablymodified without departing from the gist of the invention.

In accordance with one aspect, an ink for ink-jet recording containing abenzotriazole compound and a copper phthalocyanine pigment, furthercontains a metallic phthalocyanine compound having one or more counterions, wherein about 2 mol % to about 20 mol % of the counter ions isammonium ion, organic ammonium ion, or a combination thereof.

The ink for ink-jet recording may contain a benzotriazole compound, anda copper phthalocyanine pigment as the colorant. The copperphthalocyanine pigment is a non-water-soluble colorant coordinating acopper at the center of a phthalocyanine skeleton. Examples of thecopper phthalocyanine pigment include, but are not limited to, C.I.Pigment Blue 15:x (x is an integer of 1 to 6), C.I. Pigment Green 7,C.I. Pigment Green 36, and the like. In the point of hue, C.I. PigmentBlue 15:1, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:6, and the likemay be suitable.

The ink for ink-jet recording may contain a metallic phthalocyaninecompound, wherein about 2 mol % to about 20 mol %, about 2 mol % toabout 15 mol % of the counter ions is ammonium ion (NH₄ ⁺), organicammonium ion, or a combination thereof. The metallic phthalocyaninecompound may be added in order to prevent generation of precipitates,but many metallic phthalocyanine compounds also serve as dyes inthemselves. Examples of the metals to be coordinated include, but arenot limited to, Al, Cu, Ni, Fe, Co, and the like. But in view of hue anda color property, Cu may be suitable.

The ammonium ion and/or organic ammonium ion in the counter ions of themetallic phthalocyanine compound usually ranges from about 2 mol % toabout 20 mol %. If the amount is less than about 2 mol %, it isdifficult to effectively restrain generation of precipitates believed toresult from the benzotriazole compound, and ejecting stability of theink for ink-jet recording may be decreased. When the amount exceedsabout 20 mol %, precipitates are more likely to be generated from rubbermembers in the ink jet recording device.

The organic ammonium ion may be obtained by substituting the hydrogen(s)of NH₄₊ with 1 to 4 alkyl group(s) (a methyl group, an ethyl group, andthe like) or hydroxylalkyl group(s) (a hydroxymethyl group, ahydroxyethyl group, and the like). Examples of the organic ammonium ioninclude, but are not limited to, a monomethylammonium ion, adimethylammonium ion, a trimethylammonium ion, a tetramethylammoniumion, and the like.

The counter ions of a metallic phthalocyanine compound may besubstituted with ammonium ion (NH₄ ⁺) and/or organic ammonium ion bytreating a metallic phthalocyanine compound having a counter ion such asan alkali metal ion with aqueous ammonia and/or an aqueous solution oforganic ammonium hydroxide. The amount of the counter ions in a metallicphthalocyanine compound may be measured with a commercially availablecation chromatography apparatus.

A suitable metallic phthalocyanine compound may be a copperphthalocyanine dye in which about 2 mol % to about 20 mol % of thecounter ions is ammonium ion (NH₄ ⁺) and/or organic ammonium ion.

Suitable copper phthalocyanine dye includes, but are not limited to,C.I. Direct Blue 86, C.I. Direct Blue 199, and the like. In the pointsof a color and light fastness, C.I. Direct Blue 199 may be suitable.

C.I. Direct Blue 199 may be, for example, a copper phthalocyanine dyerepresented by the following general formula (1).

In the general formula (1), Pc(Cu) represents a copper phthalocyaninenucleus represented by the general formula (2); and substituent SO₃Ygroup (where Y represents a counter ion; Y includes, but are not limitedto, a hydrogen ion, a lithium ion, a sodium ion, a potassium ion, anammonium ion, an organic ammonium ion, or the like). Substituent SO₃Ygroup and each substituent SO₂NH₂ group are present on any of the fourbenzene rings A, B, C and D in the copper phthalocyanine nucleusrepresented by the general formula (2).

C.I. Direct Blue 199 may be produced by known methods, for example, by aknown copper phthalocyanine substitution method containing the followingsteps (i) and (ii).

Step (i):

A copper phthalocyanine may be chlorosulfonated with a chlorosulfonatingagent. For example, a mixture of chlorosulfonic acid and a chlorinatingagent (phosphorus oxychloride or phosphorus trichloride) may be used asthe chlorosulfonating agent. The molar ratio of the chlorosulfonic acidto the copper phthalocyanine compound (chlorosulfonic acid:copperphthalocyanine compound) may be within the range of about 5:1 to about200:1. The molar ratio of the chlorinating agent to the copperphthalocyanine (chlorinating agent:copper phthalocyanine) may be withinthe range of about 0.5:1 to about 10:1.

This chlorosulfonating reaction may be carried out at a temperatureranging about 90° C. to about 180° C. for about 0.5 hours to about 16hours. The reaction time of the chlorosulfonating reaction generallydepends upon the reaction temperature. When the reaction temperature ishigher, the reaction time usually is shorter. When the reactiontemperature is lower, the reaction time usually is longer. The moresuitable temperature and time for chlorosulfonating reaction may be inthe range of about 135° C. to about 145° C. for about 1.5 hours to about5 hours.

Further, the chlorosulfonating agent may contain a sulfuric acid. Whenthe chlorosulfonating agent contains a sulfuric acid, the molar ratio ofthe sulfuric acid to the copper phthalocyanine compound (sulfuricacid:copper phthalocyanine compound) usually is within the range ofabout 0.3:1 to about 2:1.

Step (ii):

Subsequently, the product obtained in step (i) may be condensed withammonia and/or organic amine so that at least a part of the counter ionsbecomes ammonium ion or organic ammonium ion to obtain C.I. Direct Blue199 in which about 2 mol % to about 20 mol % of the counter ions isammonium ion and/or organic ammonium ion.

Examples of this step are carried out using about 3 wt. % to about 35wt. % of ammonium hydroxide and/or organic ammonium hydroxide at areaction temperature of about 0° C. to about 50° C. Generally, thereaction time depends upon the reaction temperature. When the reactiontemperature is higher, the reaction time usually is shorter. When thereaction temperature is lower, the reaction time usually is longer. Themore suitable temperature and time for condensation reaction may be inthe range of about 0° C. to about 45° C. for about 0.5 hours to about 24hours.

The amount of the copper phthalocyanine pigment in the ink may bedetermined according to the performance and characteristics required ofthe ink. The amount of the copper phthalocyanine pigment may be about0.05 wt. % to about 5 wt. % based on the total weight of the ink. Othercolorants may also be used in combination.

In the ink, the copper phthalocyanine pigment usually is added as apigment dispersion obtained by dispersing in an aqueous medium with adispersant or a surfactant. Dispersants conventionally used in thepreparation of a pigment dispersion, for example, polymer dispersantsmay be used. The polymer dispersants include natural polymers andsynthetic polymers. Examples of natural polymers include, but are notlimited to, protein such as glue, gelatin, casein, albumin, and thelike; natural rubber such as gum arabic, tragacanth gum, and the like;glucoside such as saponin, and the like; alginic acid derivative such asalginic acid, propylene glycol alginate ester, triethanolamine alginate,ammonium alginate, and the like; cellulose derivative such as methylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose, ethylhydroxycellulose, and the like. Examples of synthetic polymers include, but arenot limited to, polyvinyl alcohol; polyvinyl pyrrolidone; acrylic resinsuch as polyacrylic acid, acrylic acid-acrylonitrile copolymer,potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic estercopolymer, acrylic acid-acrylic ester copolymer, and the like;styrene-(meth)acrylic resin such as styrene-acrylic acid copolymer,styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylicester copolymer, styrene-α-methylstyrene-acrylic acid copolymer,styrene-α-methylstyrene-acrylic acid-acrylic ester copolymer, and thelike; vinyl acetate copolymer such as vinyl acetate-ethylene copolymer,vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleicester copolymer, vinyl acetate-crotonic acid copolymer, vinylacetate-acrylic acid copolymer, and the like; styrene-maleic acidcopolymer; styrene-maleic anhydride copolymer; vinyl naphthalene-acrylicacid copolymer; vinyl naphthalene-maleic acid copolymer; and salts ofthese polymers. Of these polymers, copolymers of a monomer having ahydrophobic group and a monomer having a hydrophilic group, and polymerscomprising a monomer having both a hydrophobic group and a hydrophilicgroup in the molecular structure may be especially suitable.

The total amount of the copper phthalocyanine pigment and the metallicphthalocyanine compound to the amount of the ink may be usually about0.1 wt. % to about 5 wt. % based on the total weight of the ink.

In connection with the weight ratio of the copper phthalocyanine pigmentto the metallic phthalocyanine compound in the ink, ozone resistancegenerally is decreased when the ratio of the copper phthalocyaninepigment is relatively small. On the other hand, precipitation may not beeffectively restrained when the ratio is too large. The weight ratio maybe usually about 70:30 to about 95:5.

The ink may further contain a benzotriazole compound as an anticorrosiveagent for the prevention of rusts ascribable to contact of the ink withthe metallic members constituting ink-jet heads (in particular, a 42alloy (a nickel-iron alloy containing 42% of nickel)). Examples ofbenzotriazole compounds include, but are not limited to,1H-benzotriazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole,sodium salts of these benzotriazole compounds, potassium salts of thesebenzotriazole compounds, and the like.

The amount of the benzotriazole compound in the ink usually is at leasta minimum amount that provides a rust preventing effect. Excessiveamounts may increase the likelihood that precipitates may be generated.Given these considerations, the amount of the benzotriazole compoundusually ranges from about 0.01 wt. % to about 0.5 wt. %, often fromabout 0.05 wt. % to about 0.2 wt. %, based on the total weight of theink.

Water and water-soluble organic solvents that are the constituents ofthe ink are described below.

Ion exchange water which has low salts may be suitable. The amount ofwater in the ink depends upon the amount of other components, and theamount of water usually ranges from about 10 wt. % to about 90 wt. %,often from about 40 wt. % to about 80 wt. %, based on the total weightof the ink.

A water-soluble organic solvent may contain a humectant for mainlypreventing drying of the ink at the tip of the nozzle of ink-jet head,and/or a penetrant for mainly controlling drying speed of ink onrecording paper.

Examples of humectants include, but are not limited to, lower alcoholssuch as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropylalcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and thelike; polyhydric alcohols such as 1,3-butanediol, 1,5-pentanediol,1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 1,2,4-butanetriol,1,2,3-butanetriol, pentantriol, and the like; alkylene glycol such asethylene glycol, diethylene glycol, triethylene glycol, propyleneglycol, dipropylene glycol, tripropylene glycol, butylene glycol,thiodiglycol, hexylene glycol, and the like; polyalkylene glycol such aspolyethylene glycol, polypropylene glycol, and the like; amide such asformamide, N-methylformamide, N,N-dimethylformamide, dimethylacetamide,and the like; amine such as monoethanolamine, diethanolamine,triethanolamine, monoethylamine, diethylamine, triethylamine, and thelike; ketone or keto alcohol such as acetone, diacetone alcohol, and thelike; ether such as tetrahydrofuran, dioxane, and the like; pyrrolidonessuch as 2-pyrrolidone, N-methyl-2-pyrrolidone,N-hydroxyethyl-2-pyrrolidone, and the like; a nitrogen-containingheterocyclic compound such as 1,3-dimethylimidazolidinone,ε-caprolactam, and the like; a sulfur-containing compound such asdimethyl sulfoxide, sulforan, thiodiethanol and the like; and the like.Of these humectants, polyhydric alcohols such as alkylene glycol,glycerin, and the like may be suitable.

The amount of the humectant in the ink usually ranges from 0 wt. % toabout 95 wt. %, often from about 10 wt. % to about 80 wt. %, or fromabout 10 wt. % to about 50 wt. %, based on the total weight of the ink.Humectants may be used alone, or two or more kinds may be used incombination.

Examples of penetrants include, but are not limited to, ethylene glycolmethyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether,ethylene glycol butyl ether, diethylene glycol methyl ether, diethyleneglycol ethyl ether, diethylene glycol propyl ether, diethylene glycolbutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethylether, diethylene glycol dipropyl ether, diethylene glycol dibutylether, triethylene glycol methyl ether, triethylene glycol ethyl ether,triethylene glycol propyl ether, tiethylene glycol butyl ether,triethylene glycol dimethyl ether, triethylene glycol diethyl ether,triethylene glycol dipropyl ether, triethylene glycol dibutyl ether,propylene glycol methyl ether, propylene glycol ethyl ether, propyleneglycol propyl ether, propylene glycol butyl ether, dipropylene glycolmethyl ether, dipropylene glycol ethyl ether, dipropylene glycol propylether, dipropylene glycol butyl ether, dipropylene glycol dimethylether, dipropylene glycol diethyl ether, dipropylene glycol dipropylether, dipropylene glycol dibutyl ether, tripropylene glycol methylether, tripropylene glycol ethyl ether, tripropylene glycol propylether, tripropylene glycol butyl ether, tripropylene glycol dimethylether, tripropylene glycol diethyl ether, tripropylene glycol dipropylether, tripropylene glycol dibutyl ether, and the like.

The amount of the penetrant in the ink usually ranges from 0 wt. % toabout 20 wt. %, often from about 0.1 wt. % to about 15 wt. %, or fromabout 1 wt. % to about 10 wt. %, based on the total weight of the ink.When an excessive amount of penetrant is present, the penetrability ofthe ink to recording paper may become too high, which may causeblurring. Penetrants may be used alone, or two or more kinds may be usedin combination.

The ink may contain, if necessary, conventionally known additives, forexample, a viscosity modifier such as polyvinyl alcohol, polyvinylpyrrolidone, water-soluble resin, and the like; a surface tensionmodifier; a pH modifier; and the like.

The ink may be prepared by adding, if necessary, water, a water-solubleorganic solvent and other additives, to the copper phthalocyaninepigment, the benzotriazole compound, and the metallic phthalocyaninecompound in which ammonium ion (NH₄₊) and/or organic ammonium ionaccounts for about 2 mol % to about 20 mol % of the counter ions.

As described above, the ink may be prepared by dissolution, dispersion,or mixture of the components according to a conventional method. Thecopper phthalocyanine pigment, dispersant and water are mixed with adisperser (for example, a ball mill, a sand mill, an attritor, a rollmill, an agitator mill, a Henschel mixer, a colloid mill, an ultrasonicwave homogenizer, a jet mill, an ang mill, and the like) to prepare ahomogeneous pigment dispersion. Subsequently, additives such as water, ahumectant, a penetrant, a viscosity modifier, a surface tensionmodifier, a pH modifier, a preservative, a mildew proofing agent, andthe like are added to the dispersion and thoroughly dissolved to preparean ink solution. After sufficiently stirring, the ink solution isfiltered to remove coarse particles and foreign matters causingclogging, whereby ink-jet recording ink may be obtained.

EXAMPLE

The following examples are provided only to illustrate certain aspectsof the description and are not intended to embody the total scope of theinvention or any aspect thereof. Variations of the examples below areintended to be included within the scope of the invention.

Examples 1 to 8, and Comparative Examples 1 to 6

Inks for ink-jet recording were prepared by homogeneously mixing the inkcomposition summarized in Table 1. Counter ions other than ammonium ionin the metallic phthalocyanine compound were monovalent metal ions suchas lithium ion, sodium ion, potassium ion, and the like.

In the measurement of ammonium ions in the metallic phthalocyaninecompound, DX-500 series (manufactured by Nippon Dionex K.K.) was used.In the measurement, IonPac® CG16 (manufactured by Nippon Dionex K.K.)was used as the separation column, the temperature of the thermostaticchamber was 45° C., CMMS III 4 mm (manufactured by Nippon Dionex K.K.)was used as the suppressor.

<<Evaluation>>

Each of the inks was tested and evaluated for storage stability(filtration test), ejecting stability, durable ejecting stability, arust preventing property, precipitation of rubber, glossiness, and ozoneresistance as described below. The results obtained are summarized inTable 1.

<Storage Stability (Filtration Test)>

After 100 ml of the ink was sealed in a glass container and allowed tostand in a thermostatic chamber at 60° C. for 14 days, 50 ml of the inkwas filtered through a hydrophilic membrane filter having a pore size of1.0 μm. The presence of precipitate on the membrane filter was observedvisually and with a microscope. Evaluation was carried out according tothe following criteria.

A: Precipitates were not present on the membrane filter.

C: Precipitates were present on the membrane filter.

<Ejecting Stability>

The ink was filled in a predetermined ink cartridge, installed in anink-jet printer-mounted digital multifunction device (DCP-110C,manufactured by Brother Industries, Ltd.), and continuous printing ofone hundred million dots (about thirty thousand sheets) was performed.Evaluation was carried out according to the following criteria.

AA: Non-ejection and ejection bending were not observed at all incontinuous printing.

A: Non-ejection or ejection bending was slightly observed in continuousprinting, and both non-ejection and ejection bending were recoveredwithin five purges.

C: Conspicuous non-ejection and ejection bending were observed incontinuous printing, and both non-ejection and ejection bending were notrecovered within five purges.

<Durable Ejecting Stability>

After the above ejecting stability test, an ink-jet printer-mounteddigital multifunction device (DCP-110C) was allowed to stand as it wasin the thermostatic chamber at 60° C. for two weeks, and then againcontinuous printing of one hundred million dots (about thirty thousandsheets) was performed. Evaluation was carried out according to thefollowing criteria.

AA: Non-ejection and ejection bending were not observed at all incontinuous printing.

A: Non-ejection or ejection bending was slightly observed in continuousprinting, and both non-ejection and ejection bending were recoveredwithin five purges.

C: Conspicuous non-ejection and ejection bending were observed incontinuous printing, and both non-ejection and ejection bending were notrecovered within five purges.

<Rust Preventing Property>

The metallic member used in the ink-jet head was processed to astrip-shape of 50 mm length, 10 mm width and 2 mm thickness to produce ametallic member sample, and a sample piece of the produced metallicmember sample was immersed in 10 ml of the ink in a sealed container,and allowed to stand in a thermostatic chamber at 60° C. for 2 weeks.After that, the immersed sample piece of metallic member sample wastaken out and observed visually and with a microscope. Evaluation wascarried out according to the following criteria.

AA: Coloring and corrosion were not observed at all.

A: Slight coloring was observed, but corrosion was not observed.

C: Coloring and corrosion were observed.

<Precipitation of Rubber>

A rubber sample processed to a strip-shape of 50 mm length, 10 mm width,and 2 mm thickness was immersed in 10 ml of the ink in a sealedcontainer, and allowed to stand in a thermostatic chamber at 60° C. for2 weeks. After that, the immersed sample was taken out. All the amountof the ink after the sample was taken out was filtered through anelectroformed filter (a pore size: 13 μm, effective filtration area: 8cm²), and the time required for filtration was measured. As the control,ink alone to which a rubber sample was not immersed was allowed to standon the same condition (60° C. for 2 weeks), filtered through anelectroformed filter of the same specification as above, and the timerequired for filtration (standard time) was found. The ratio of the timerequired for filtration of the ink having immersed the rubber sample tothe standard time was calculated and evaluation was carried outaccording to the following criteria. Incidentally, from the observationof the electroformed filter after filtration with a microscope, it wasconfirmed that as the ratio of the filtration time to the standard timewas greater, the amount of precipitates was also greater.

AA: The filtration time of less than 130% of the standard time wasrequired.

A: The filtration time of 130% or more and less than 200% of thestandard time was required.

B: The filtration time of 200% or more and less than 400% of thestandard time was required.

C: The filtration time of 400% or more of the standard time wasrequired.

<Glossiness>

The ink was filled in a predetermined ink cartridge, installed in anink-jet printer-mounted digital multifunction device (DCP-110C,manufactured by Brother Industries, Ltd.), and solid printing wasperformed on photographic glossy paper (BP60GLA, manufactured by BrotherIndustries, Ltd.). Evaluation of the image quality was carried out byvisual observation according to the following criteria.

A: The difference in glossiness was not observed between the solidprinted part and the surrounding non-printed part, or slight differencein glossiness was felt but the solid printed part was not relieved andseen evenly.

B: The difference in glossiness was observed between the solid printedpart and the surrounding non-printed part, and the solid printed partwas seen a little in relief, but not problematic in practical use.

C: The great difference in glossiness was observed between the solidprinted part and the surrounding non-printed part, and the solid printedpart was seen in relief.

<Ozone Resistance>

The ink was filled in a predetermined ink cartridge, installed in anink-jet printer-mounted digital multifunction device (DCP-110C,manufactured by Brother Industries, Ltd.), and printing evaluation wasperformed. First, as evaluation samples, gradation samples of cyan inkswere printed on photographic glossy paper (BP60GLA, manufactured byBrother Industries, Ltd.) to produce patches of various OD (opticaldensity) values. The patches were subjected to ozone resistanceevaluation test with an ozone weather meter OMS-H (manufactured by SugaTest Instruments Co., Ltd.). The patches were allowed to stand on thecondition of ozone concentration of 1 ppm, the temperature in thechamber of 24° C., and humidity in the chamber of 60% RH for 40 hours.Specifically, OD value after the ozone resistance evaluation test wasmeasured of a color patch of a cyan color print part showing OD value of1.0 before the test (however, in the case where ink whose OD value isless than 1.0, the maximum OD value). OD value was measured withSpectrolino (manufactured by Gretag Macbeth AG) (light source: D₆₅,angle of visibility: 2°, status A). By substituting the obtainedmeasurement value (OD value after the test) for the following equation,the reduction rate of OD value to the OD value before the test wascalculated.

[Reduction rate of OD value (%)]={[(OD value before the test)−(OD valueafter the test)]/(OD value before the test)}×100

The obtained reduction rate of OD value was evaluated according to thefollowing evaluation criteria. When the reduction rate of OD value wasless than 30%, ozone resistance performance in general use was judged asthe level of eligibility.

AA: The reduction rate of OD value was less than 20%.

A: The reduction rate of OD value was 20% or more and less than 30%.

B: The reduction rate of OD value was 30% or more and less than 40%.

C: The reduction rate of OD value was 40% or more.

<Overall Quality>

Considering the above evaluation results, the inks were evaluatedaccording to the following criteria.

G: All the evaluation results were AA or A.

NG: Any of the evaluation results was B or C.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ink Amount ofammonium ions (mol %) in the 13.0 5.0 3.0 10.0 2.0 20.0 8.0 19.0 counterions in metallic phthalocyanine compound Total amount of copperphthalocyanine 4.0 2.0 0.1 2.5 5.0 1.5 3.0 1.0 pigment and metallicphthalocyanine compound (wt. %) copper phthalocyanine pigment:metallic95:5 95:5 90:10 90:10 80:20 80:20 70:30 70:30 phthalocyanine compoundInk Comp. Copper C.I. Pigment Blue 15:1 3.8 — — 2.25 — — 2.1 — (wt. %)phthalocyanine C.I. Pigment Blue 15:3 — 1.9 — — 4.0 — — 0.7 pigment C.I.Pigment Blue 15:6 — — 0.09 — — 1.2 — — Metallic C.I. Direct Blue 86 0.2— 0.01 — 1.0 — 0.9 — phthalocyanine C.I. Direct Blue 199 — 0.1 — 0.25 —0.3 — 0.3 compound Glycerin 27.0 27.0 27.0 27.0 27.0 27.0 27.0 27.0Triethylene glycol butyl ether 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0Styrene-acrylic acid copolymer 3.8 1.9 0.09 2.25 4.0 1.2 2.1 0.7Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 OLFINE ® E1010*¹ 0.2 0.20.2 0.2 0.2 0.2 0.2 0.2 Water Balance Balance Balance Balance BalanceBalance Balance Balance Evaluation Storage stability (filtration test) AA A A A A A A Ejecting stability AA AA AA AA AA AA AA AA Durableejecting stability AA AA AA AA AA A AA A Rust preventing property AA AAAA AA AA AA AA AA Precipitation of rubber AA AA AA AA AA A AA AGlossiness (printing on glossy paper) A A A A A A A A Ozone resistanceAA AA AA AA AA AA A A Reduction rate of OD value (%) 7 5 12 11 17 20 2323 Overall quality G G G G G G G G Comp. Ex. 1 Comp. Ex. 2 Comp. Ex. 3Comp. Ex. 4 Comp. Ex. 5 Comp. Ex. 6 Ink Amount of ammonium ions (mol %)in 0 1.0 32.0 — 10.0 10.0 the counter ions in metallic phthalocyaninecompound Total amount of copper phthalocyanine 4.0 4.0 4.0 4.0 4.0 4.0pigment and metallic phthalocyanine compound (wt. %) copperphthalocyanine pigment:metallic 80:20 80:20 80:20 100:0 0:100 80:20phthalocyanine compound Ink Comp. Copper C.I. Pigment Blue 15:1 — 3.2 —— — 3.2 (wt. %) phthalocyanine C.I. Pigment Blue 15:3 — — 3.2 — — —pigment C.I. Pigment Blue 15:6 3.2 — — 4.0 — — Metallic C.I. Direct Blue86 0.8 — 0.8 — — 0.8 phthalocyanine C.I. Direct Blue 199 — 0.8 — — 4.0 —compound Glycerin 27.0 27.0 27.0 27.0 27.0 27.0 Triethylene glycol butylether 5.0 5.0 5.0 5.0 5.0 5.0 Styrene-acrylic acid copolymer 3.2 3.2 3.24.0 — 3.2 Benzotriazole 0.1 0.1 0.1 0.1 0.1 — OLFINE ® E1010*¹ 0.2 0.20.2 0.2 0.2 0.2 Water Balance Balance Balance Balance Balance BalanceEvaluation Storage stability (filtration test) C C A C A A Ejectingstability C C AA C AA A Durable ejecting stability C C C C AA C Rustpreventing property AA AA AA AA AA C Precipitation of rubber AA AA C AAAA AA Glossiness (printing on glossy paper) A A A C A A Ozone resistanceAA AA AA AA C AA Reduction rate of OD value (%) 18 18 19 2 66 16 Overallquality NG NG NG NG NG NG *¹Acetylene glycol type surfactant; activeingredient is 100 wt. %; manufactured by Nissin Chemical Indistry Co.,Ltd.

<Consideration of the Results Obtained in Examples and ComparativeExamples>

In the ink in Example 1 (the total amount of the copper phthalocyaninepigment and the metallic phthalocyanine compound (hereinafter referredto as the total amount of phthalocyanines) is 4.0 wt. %), 13.0 mol % ofthe counter ions of C.I. Direct Blue 86 of a metallic phthalocyaninecompound was ammonium ion, so that precipitates were not generated andthe ink was stably ejected from start to finish. Because the inkcontained benzotriazole as the anticorrosive agent, corrosion of themetallic members did not occur. Further, because the amount of theammonium ion of the counter ions of C.I. Direct Blue 86 was 13.0 mol %,there was no precipitation of components from the rubber member. Becausethe amount of C.I. Direct Blue 86 in the total amount of phthalocyanineswas 5%, glossiness in printing on glossy paper was good. The amount ofC.I. Pigment Blue 15:1 of a copper phthalocyanine pigment having goodozone resistance accounted for 95% in the total amount ofphthalocyanines, so that the ink had good ozone resistance.

In the ink in Example 2 (the total amount of phthalocyanines=2.0 wt. %),5.0 mol % of the counter ions of C.I. Direct Blue 199 of a metallicphthalocyanine compound is ammonium ion, so that precipitates were notgenerated and the ink was stably ejected from start to finish. Becausethe ink contained benzotriazole as the anticorrosive agent, corrosion ofthe metallic members did not occur. Further, because the amount of theammonium ion of the counter ions of C.I. Direct Blue 199 was 5.0 mol %,there was no precipitation of components from the rubber member. Becausethe amount of C.I. Direct Blue 199 in the total amount ofphthalocyanines was 5%, glossiness in printing on glossy paper was good.The amount of C.I. Pigment Blue 15:3 of a copper phthalocyanine pigmenthaving good ozone resistance accounted for 95% in the total amount ofphthalocyanines, so that the ink had good ozone resistance.

In the ink in Example 3 (the total amount of phthalocyanines=0.1 wt. %),3.0 mol % of the counter ions of C.I. Direct Blue 86 of a metallicphthalocyanine compound was ammonium ion, so that precipitates were notgenerated and the ink-jet recording ink was stably ejected from start tofinish. Because the ink contained benzotriazole as the anticorrosiveagent, corrosion of the metallic members did not occur. Further, becausethe amount of the ammonium ion of the counter ions of C.I. Direct Blue86 was 3.0 mol %, there was no precipitation of components from therubber member. Because the amount of C.I. Direct Blue 86 in the totalamount of phthalocyanines was 10%, glossiness in printing on glossypaper was good. The amount of C.I. Pigment Blue 15:6 of a copperphthalocyanine pigment having good ozone resistance accounted for 90% inthe total amount of phthalocyanines, so that the ink had good ozoneresistance.

In the ink in Example 4 (the total amount of phthalocyanines=2.5 wt. %),10.0 mol % of the counter ions of C.I. Direct Blue 199 of a metallicphthalocyanine compound was ammonium ion, so that precipitates were notgenerated and the ink was be stably ejected from start to finish.Because the ink contains benzotriazole as the anticorrosive agent,corrosion of the metallic members did not occur. Further, because theamount of the ammonium ion of the counter ions of C.I. Direct Blue 199was 10.0 mol %, there was no precipitation of components from the rubbermember. Because the amount of C.I. Direct Blue 199 in the total amountof phthalocyanines was 10%, glossiness in printing on glossy paper wasgood. The amount of C.I. Pigment Blue 15:1 of a copper phthalocyaninepigment having good ozone resistance accounted for 90% in the totalamount of phthalocyanines, so that the ink had good ozone resistance.

In the ink in Example 5 (the total amount of phthalocyanines=5.0 wt. %),2.0 mol % of the counter ions of C.I. Direct Blue 86 of a metallicphthalocyanine compound was ammonium ion, so that precipitates were notgenerated and the ink was stably ejected from start to finish. Becausethe ink contained benzotriazole as the anticorrosive agent, corrosion ofthe metallic members did not occur. Further, because the amount of theammonium ion of the counter ions of C.I. Direct Blue 86 was 2.0 mol %,there was no precipitation of components from the rubber member. Becausethe amount of C.I. Direct Blue 86 in the total amount of phthalocyanineswas 20%, glossiness in printing on glossy paper was good. The amount ofC.I. Pigment Blue 15:3 of a copper phthalocyanine pigment having goodozone resistance accounted for 80% in the total amount ofphthalocyanines, so that the ink had good ozone resistance.

In the ink in Example 6 (the total amount of phthalocyanines=1.5 wt. %),20.0 mol % of the counter ions of C.I. Direct Blue 199 of a metallicphthalocyanine compound was ammonium ion, so that precipitates were notgenerated and the ink was stably ejected from start to finish. Becausethe ink contained benzotriazole as the anticorrosive agent, corrosion ofthe metallic members did not occur. Further, because the amount of theammonium ion of the counter ions of C.I. Direct Blue 199 was 20.0 mol %,there was very little precipitation of components from the rubbermember. Because the amount of C.I. Direct Blue 199 in the total amountof phthalocyanines was 20%, glossiness in printing on glossy paper wasgood. The amount of C.I. Pigment Blue 15:6 of a copper phthalocyaninepigment having good ozone resistance accounted for 80% in the totalamount of phthalocyanines, so that the ink had good ozone resistance.

In the ink in Example 7 (the total amount of phthalocyanines=3.0 wt. %),8.0 mol % of the counter ions of C.I. Direct Blue 86 of a metallicphthalocyanine compound was ammonium ion, so that precipitates were notgenerated and the ink was stably ejected from start to finish. Becausethe ink contained benzotriazole as the anticorrosive agent, corrosion ofthe metallic members did not occur. Further, because the amount of theammonium ion of the counter ions of C.I. Direct Blue 86 was 8.0 mol %,there was no precipitation of components from the rubber member. Becausethe amount of C.I. Direct Blue 86 in the total amount of phthalocyanineswas 30%, glossiness in printing on glossy paper was good. The amount ofC.I. Pigment Blue 15:1 of a copper phthalocyanine pigment having goodozone resistance accounts for 70% in the total amount ofphthalocyanines, so that the ink had good ozone resistance.

In the ink in Example 8 (the total amount of phthalocyanines=1.0 wt. %),19.0 mol % of the counter ions of C.I. Direct Blue 199 of a metallicphthalocyanine compound was ammonium ion, so that precipitates were notgenerated and the ink was stably ejected from start to finish. Becausethe ink contained benzotriazole as the anticorrosive agent, corrosion ofthe metallic members did not occur. Further, because the amount of theammonium ion of the counter ions of C.I. Direct Blue 199 was 19.0 mol %,there was very little precipitation of components from the rubbermember. Because the amount of C.I. Direct Blue 199 in the total amountof phthalocyanines was 30%, glossiness in printing on glossy paper wasgood. The amount of C.I. Pigment Blue 15:3 of a copper phthalocyaninepigment having good ozone resistance accounted for 70% in the totalamount of phthalocyanines, so that the ink had good ozone resistance.

In the ink in Comparative Example 1 (the total amount ofphthalocyanines=4.0 wt. %), benzotriazole is contained as theanticorrosive agent, so that corrosion of the metallic members did notoccur. Because ammonium ion and organic ammonium ion were not containedin C.I. Direct Blue 86 as the counter ions, there was no precipitationof components from the rubber member. The amount of C.I. Direct Blue 86in the total amount of phthalocyanines was 20%, so that glossiness inprinting on glossy paper was good. The amount of C.I. Pigment Blue 15:6of a copper phthalocyanine pigment having good ozone resistanceaccounted for 80% in the total amount of phthalocyanines, so that theink had good ozone resistance. However, because ammonium ion and organicammonium ion as the counter ions were not contained in C.I. Direct Blue86, precipitation was not restrained and precipitates were generated.Therefore, the ink was not stably continuously ejected.

In the ink in Comparative Example 2 (the total amount ofphthalocyanines=4.0 wt %), benzotriazole was contained as theanticorrosive agent, so that corrosion of the metallic members did notoccur. Because the amount of the ammonium ion of the counter ions ofC.I. Direct Blue 199 was 1.0 mol %, there was no precipitation ofcomponents from the rubber member. The amount of C.I. Direct Blue 199 inthe total amount of phthalocyanines was 20%, so that glossiness inprinting on glossy paper was good. The amount of C.I. Pigment Blue 15:1of a copper phthalocyanine pigment having good ozone resistanceaccounted for 80% in the total amount of phthalocyanines, so that theink had good ozone resistance. However, the amount of the ammonium ionof the counter ions of C.I. Direct Blue 199 was 1.0%, so thatprecipitation was not restrained and precipitates were generated.Therefore, the ink was not stably continuously ejected.

In the ink in Comparative Example 3 (the total amount ofphthalocyanines=4.0 wt. %), 32.0 mol % of the counter ions of C.I.Direct Blue 86 was ammonium ion, so that precipitates were not generatedand the ink was stably ejected immediately after feeding of ink. Becausethe ink contained benzotriazole as the anticorrosive agent, corrosion ofthe metallic members did not occur. Because the amount of C.I. DirectBlue 86 in the total amount of phthalocyanines was 20%, glossiness inprinting on glossy paper was good. Further, the amount of C.I. PigmentBlue 15:3 of a copper phthalocyanine pigment having good ozoneresistance accounted for 80% in the total amount of phthalocyanines, theink had good ozone resistance. However, the amount of the ammonium ionof the counter ions of C.I. Direct Blue 86 was 32 mol %, which led toprecipitation of components from the rubber member. The ink was notstably ejected after the durability test.

In the ink in Comparative Example 4 (the total amount ofphthalocyanines=4.0 wt. %), benzotriazole was contained as theanticorrosive agent, so that corrosion of the metallic members did notoccur. Because ammonium ion was not present as the counter ion in themetallic phthalocyanine compound, there was no precipitation ofcomponents from the rubber member. However, because a metallicphthalocyanine compound was not used and C.I. Pigment Blue 15:6 of acopper phthalocyanine pigment alone was used, precipitation was notrestrained and precipitates were generated. Therefore, the ink was notstably continuously ejected. Further, the difference in glossiness wasgreat between the printed part and the non-printed part when printing onglossy paper, and the printed part was seen as relieved.

In the ink in Comparative Example 5 (the total amount ofphthalocyanines=4.0 wt. %), 10.0 mol % of the counter ions of C.I.Direct Blue 199 was ammonium ion, so that precipitates were notgenerated and the ink was stably ejected from start to finish. Becausethe ink contained benzotriazole as the anticorrosive agent, corrosion ofthe metallic members did not occur. Because the amount of the ammoniumion of the counter ions of C.I. Direct Blue 199 was 10.0 mol %, therewas no precipitation of components from the rubber member. The ink inComparative Example 5 is the ink using C.I. Direct Blue 199 alone, sothat glossiness in printing on glossy paper was good. However, C.I.Direct Blue 199 was inferior in ozone resistance, so that ozoneresistance of the ink was insufficient.

In the ink in Comparative Example 6 (the total amount ofphthalocyanines=4.0 wt. %), 10.0 mol % of the counter ions of C.I.Direct Blue 86 was ammonium ion, so that precipitates were not generatedand the ink was stably ejected immediately after feeding of ink. Theamount of the ammonium ion of the counter ions of C.I. Direct Blue 86was 10.0 mol %, so that there was no precipitation of components fromthe rubber member. The amount of C.I. Direct Blue 86 in the total amountof phthalocyanines was 20%, so that glossiness in printing on glossypaper was good. The amount of C.I. Pigment Blue 15:1 of a copperphthalocyanine pigment having good ozone resistance accounted for 80% inthe total amount of phthalocyanines, so that the ink had good ozoneresistance. However, because the ink did not contain an anticorrosiveagent, metal corrosion occurred at the head parts. Therefore the ink wasnot stably continuously ejected due to presence of the rust.

The invention is not limited to the embodiments described in theExamples, which are provided for illustrative purposes only. Thematerial substances, their amounts used, and the conditions of producingthem may be varied and modified without departing from the spirit andthe scope of the invention as described and claimed herein.

1. An ink for ink-jet recording comprising a benzotriazole compound anda copper phthalocyanine pigment, wherein the ink further comprises ametallic phthalocyanine compound having one or more counter ions,wherein about 2 mol % to about 20 mol % of the counter ions is selectedfrom the group consisting of ammonium ions, organic ammonium ions, andcombinations thereof.
 2. The ink according to claim 1, wherein a totalamount of the copper phthalocyanine pigment and the metallicphthalocyanine compound is from about 0.1 wt. % to about 5 wt. % basedon total weight of the ink.
 3. The ink according to claim 1, wherein aweight ratio of the copper phthalocyanine pigment to the metallicphthalocyanine compound is from about 70:30 to about 95:5.
 4. The inkaccording to claim 1, wherein the copper phthalocyanine pigment is C.I.Pigment Blue 15:x, wherein x is an integer of 1 to
 6. 5. The inkaccording to claim 4, wherein the copper phthalocyanine pigment isselected from the group consisting of C.I. Pigment Blue 15:1, C.I.Pigment Blue 15:3, C.I. Pigment Blue 15:6, and combinations thereof. 6.The ink according to claim 1, wherein the metallic phthalocyaninecompound is a copper phthalocyanine dye.
 7. The ink according to claim6, wherein the copper phthalocyanine dye is C.I. Direct Blue
 86. 8. Theink according to claim 6, wherein the copper phthalocyanine dye is C.I.Direct Blue
 199. 9. The ink according to claim 8, wherein the C.I.Direct Blue 199 has a structure represented by General Formula (1):

wherein Y represents a counter ion selected from the group consisting ofa hydrogen ion, a lithium ion, a sodium ion, a potassium ion, anammonium ion, and an organic ammonium ion; and Pc(Cu) represents acopper phthalocyanine nucleus represented by General Formula (2):

wherein SO₃Y group and each SO₂NH₂ group is present on any of the fourbenzene rings A, B, C and D in the copper phthalocyanine nucleus. 10.The ink according to claim 1, wherein the benzotriazole compound isselected from the group consisting of 1H-benzotriazole,4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, sodium saltsthereof, and potassium salts thereof.
 11. The ink according to claim 10,wherein the amount of the benzotriazole compound is from about 0.01 wt.% to about 0.5 wt. % based on the total weight of the ink.
 12. The inkaccording to claim 10, wherein the amount of the benzotriazole compoundis from about 0.05 wt. % to about 0.2wt. %, based on the total weight ofthe ink.
 13. A method of improving corrosion resistance in an ink forink-jet recording comprising a benzotriazole compound and a copperphthalocyanine pigment, the method comprising adding to the ink ametallic phthalocyanine compound having one or more counter ions whereinabout 2 mol % to about 20 mol % of the counter ions is selected from thegroup consisting of ammonium ions, organic ammonium ions, andcombinations thereof.
 14. The method according to claim 13, wherein atotal amount of the copper phthalocyanine pigment and the metallicphthalocyanine compound is from about 0.1 wt. % to about 5 wt. % basedon the total weight of the ink.
 15. The ink according to claim 13,wherein a weight ratio of the copper phthalocyanine pigment to themetallic phthalocyanine compound is from about 70:30 to about 95:5. 16.The method according to claim 13, wherein the metallic phthalocyaninecompound is a copper phthalocyanine dye.
 17. A method of avoiding theformation of precipitates in an ink for ink-jet recording comprising abenzotriazole compound and a copper phthalocyanine pigment, the methodcomprising adding to the ink a metallic phthalocyanine compound havingone or more counter ions wherein about 2 mol % to about 20 mol % of thecounter ions is selected from the group consisting of ammonium ions,organic ammonium ions, and combinations thereof.
 18. The methodaccording to claim 17, wherein a total amount of the copperphthalocyanine pigment and the metallic phthalocyanine compound is fromabout 0.1 wt. % to about 5 wt. % based on the total weight of the ink.19. The ink according to claim 17, wherein a weight ratio of the copperphthalocyanine pigment to the metallic phthalocyanine compound is fromabout 70:30 to about 95:5.
 20. The method according to claim 17, whereinthe metallic phthalocyanine compound is a copper phthalocyanine dye.